Institute for Soldier Nanotechnologies, 500 Technology Square, Cambridge, MA, 02139, USA.
Department of Chemistry, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
Nat Commun. 2022 May 27;13(1):2775. doi: 10.1038/s41467-022-29811-6.
In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents.
在当代有机合成中，人们利用那些在辐照下能够进入强氧化态和/或强还原态的物质来促进强大且前所未有的转化。然而，由于缺乏用于固定、分离和重复使用这些不同催化剂的通用技术，光驱动反应在大规模工艺中的应用仍然很少见。在这里，我们报告了一类新的光活性有机聚合物，它们将小分子染料的灵活性与固相催化剂的操作优势和可回收性结合在一起。这些聚合物在某些非极性有机溶剂中的溶解度支持它们容易加工成各种不同的异相形式。活性位点嵌入在多孔微结构中，显示出更高的反应活性，通过聚合物中激发态和带电物质的迁移进一步增强。这些材料的物理和光化学性质的独立可调性为将现代光氧化还原催化剂转变为活性异相等价物提供了一个方便、可推广的平台。
